Separation of fluid mixtures



E. c. MILLER 2,890,571

SEPARATION oF FLUID Mxx'ruREs 5 sheetssnet 1 June 16, 1959 Filed Aug. 20, 1956 E. C. MILLER SEPARATION OF' FLUID MIXTURES June 16,I 1959 3 Sheets-Sheet'I 2 Filed Aug. 20.. 1956 N .bfi

INVENTOR. E C MILLER A TTORNEYS mmPmm ZOU DMCDQJDOMN- June 16, 1959 E. c. MILLER SEPARATIQII oF FLUID IIIxTuREs 3 Sheets-Sheet 3 Filed Aug. 20, 1956 N m T C A R CI E R 1V F O X E D N s l/ V E N A H Il E M .,/o/o .r /o f O O O O O 4 3 2 7.o INDEX OF REFRACTION, (N

IN VEN TOR.

oas a /O INDEX oF REFRACTION, (N-I) x Io4 MOZ mP CONCENTRATION FIG. 3

A Tron/viv;

nited States Patent 2,890,571 SEPARATION on FLUID MIXTURES Eimerl C'. Miner', Barnesviue, okla., assignor to Phniips Petroleum Company, a corporation of Delaware Application August 20, 1956, Serial No. 604,991 7 Claims. (Cl. 62-37) This invention relates to a method `of and apparatus for removing selected constituents from fluid mixtures.

It is known that ethylene and other low molecular weight unsaturated hydrocarbons can be produced advantageously by the thermal cracking of light saturated hydrocarbons, such as butane. The eiuent from such a cracking process comprises vapors which have boiling points over a wide temperature range. One convenient system for separating desired gases, such as ethylene, involves initially removing the C4 and heavier hydrocarbons in an absorption column. The effluent from this column can be fractionated to remove methane and other components which have boiling points lower than the boiling point of methane. The kettle product from this fractionation column can further be fractionated to separate the gaseous mixture into streams of selected constituents.

In accordance with the present invention, there is provided a method for separating a uix mixture containing methane and other components having higher boiling points into a rst stream which is substantially free of methane and a second stream which contains methane and other components in the fluid mixture which have boiling points lower than the boiling point of methane. This separation is accomplished by the use of a fractionation column. The overhead stream removed from the column comprises primarily methane and other constituents having lower boiling points. The kettle product is vsubstantially free of methane. It has been discovered, in accordance with the present invention, that the refractive index Aof the uid mixture in the lower region of the column is indicative of the methane concentration in the mixture. This discovery is surprising because the material in the lower region of the column normally contains a large number of constituents other than methane. The refractive index of a sample stream removed from the lower region of the column is measured to provide a signal which is representative of the methane concentration at this region of the column, This signal is employed to control theV operation of the column to maintain the methane concentration in the kettle product within selected limits. The control can be accomplished advantageouslyfby regulating the amount of overhead gases removed from'the system.

Accordingly, it is an object of this invention to provide a novel method of and apparatus for separating fluid mixtures.

Another object is to provide a control system for the separationof fluid mixtures which is based upon a measurement of the refractive index of a sample stream removed from the separating means.

Another object is to provide a method of and apparatus v for separating a fluid mixture containing methane and other components of higher boiling points into a iirst stream substantially free of methane and a second stream containing methane and any components present in the fs ICC uid mixture which have boiling points lower than the boiling points of methane.

Other objects, advantages and features of the invention should become apparent from the following detailed description which is taken in conjunction with the accompanying drawing in which: p

Figure l is a schematic representation of apparatus which is provided in accordance with this invention to crack hydrocarbons and separate the effluent vapors.

Figure 2 is a schematic drawing of a differential refractrometer which can b'e employed to control the operation of the fractionation column of Figure 1.

Figure 3 is a graphical representation of the concentration and index of refraction of materials in the lower region of the fractionation column of Figure l.

Figure 4 is a graphical representation of the concentration of methane as a function of the refractive index of the fluid mixture in the lower portion of the fractionation column of Figure l.

Referring now to the drawing in detail and to Figure 1 in particular, a hydrocarbon feed stream to be cracked is supplied by a conduit 10 which communicates through a vaporizer 11 with the inlet of a cracking furnace 12. A diluent, such as steam, is added to conduit 10 by means of a conduit 13. Furnace 12 has an elongated pipe 14 in the upper portion thereof which communicates with a second elongated pipe 15 in the lower portion. Heat is supplied to these pipes by a plurality of burners which are mounted in the side walls of the furnace. Pipe 15 communicates with an outlet conduit 16. Water is added to conduit 16 by means of a conduit 17 in order to quench the furnace eluent. Conduit 16 communicates with the inlet of a quench drum 56. A cool oil is sprayed into drum 56 by means of an inlet conduit 18 to cool further the furnace eiuent. The heated oil is removed from the bottom of drum 56 through an outlet conduit 19, cooled, and subsequently recycled to drum 56. Vapors from drum 56 are directed through a conduit 21 and a cooler 22 to a knock-out drum- 23. Any condensed material is removed from drum 23 through a conduit 24. Vapors are removed from drum 23 through a conduit 25 which communicates with the inlet of a compressor 26. The outlet of compressor 26 is connected by means of a conduit 27 to the inlet of an absorber 29.

A lean oil is supplied to the upper regionof absorber 29 by means of a conduit y30. The rich oil is removed from absorber 29 through a conduit 31. Absorber 29 normally is' operated so that substantially all of the C4 and heavier hydrocarbons are absorbed by the oil and removed through conduit 31. The effluent gases from absorber 29 are removed through a conduit 32 which has a drier 33 therein. Conduit 32 communicates at a second end with the inlet of a fractionation column 35 which is employed to remove methane and lighter gases from the gaseous efuent from absorber 29.

Column 35 is provided with a cooling coil 36 in the upper region and a heating coil 37 in the lower region. These coils provide the desired temperature differential to accomplish the separation of the fluid mixture. Vapors are removed from the top of column 35 through a conduit 38 which communicates through a condenser 39 with a reux vaccumulator 40. The condensed liquid is directed from accumulator 40 back to column 35 through a reux conduit 41. The vapor in accumulator 40 is removed through a conduit 43 which communicates with a liquidvapor separator 44 through heat exchangers 45 and 46 and a pressure reducing valve 47. Condensed vapors are returned from separator 44 to accumulator 40 through a conduit 48'which passes through heat exchanger 45. Cooled vapors from separator 44 are removed through an outlet conduit 50 which passes through heat exchanger 46. A control valve,5r1ris provided intconduit 5,0 to permit the amount of effluent gas withdrawn to be regulated.

A. kettle products removed from wlumn through an outlet conduit 52. A cond-uit '53 communicates between a lower region of column 35 and the inlet of a refractrometer 54 in order to provide a sample stream to the refractrometer. This sample lis vented through a conduit 55. Refractrometer 54 provides an output signal which is representative of the refractive index of the sample stream removed from column 3 5. This signal controls valve 51 in the manner described in detail hereinafter to regulate the operation of the column so that the desired fluid separation is maintained.

A suitable instrument which be employed to measure: the refractive index of thev samplenstream is illustrated in Figure 2 This .instrument comprises a source of light 60 which is mountedin ahousing 61. Source 60 can be an ordinary incan descentA bulb,whic h emits radiation in the visible spectrum., A PQYQD o f the light emitted from source 60 passes through aiirstaperture 62 and a converging lens 63. A narrow beam of this light emerges from housing 61 through a second aperture 64. This light beam is directed through a refractrometer cell assembly 66. The purpose of aperture 62 is to reduce the total radiation transmitted from light source 60 in order to minimize heating of the cell assembly. The filament of source 60 is located slightly beyond the focal point of lens 63 which in turn is positioned in close proximity to aperture 64.

Cell assembly 66 comprises first and second chambers 67 and 68 which are separated by a plate 69 of radiation transparent material. y Plate 69 is disposed at an angle other than 90 with respect .to the axis of the beam of radiation transmitted through a cell assembly. A converging lens 71 comprises the inlet window of chamber 68 and a converging lens 72 comprises the outlet window of chamber 67. The components thus far described are arranged such that aperture 64 is at the effective principal Afocus of lens 71. This results in a parallel beam of light being transmitted through the cell assembly.

The light beam emerging from lens 72 enters a glass prism 75 which is positioned such that -its front surface is substantially perpendicular to the light beam. The light is twice reflected within prism 75 and emerges in a direction so as to pass through a rotatable glass block 76. The light beam then strikes the apex of a second prism 77. A radiation detecting unit which comprises photovoltaic cells 78 and 79 is positioned so that a light beam striking the apex of prism 77 is divided into two beams of equal magnitude which impinge upon the two cells. The output voltages of cells 78 and 79 are connected in opposition to one another to the input terminals of a converter 81. The diiferential output signal from the two cells is thus converted into a corresponding alternating signal which Iis applied to the input terminals of an amplifier 82. Converter 81 is energized from a source of alternating current 84 which is applied across the primary winding 85 of a transformer 86 through a switch 87. The rst secondary winding 88 of transformer 86 is connected to converter 81 so that the frequency of the signal applied to amplifier 82 is the same as that of current source 84. The output signal of amplitier 82 is applied to the first winding 89 of a reversible two phase induction motor 90dY A second secondary winding 92 of transformer 86 is connected across the seeond motor winding 93 through a capacitor 94. This results in the two signals applied to the motor windings being either 90 or 270 out of phase with one another depending upon the polarity of the input signal applied to converter 81. Converter 81, amplifier 82 and motor 9.0 can be of the type described in The Electronic Control Handbook, Batcher and Moulic, Caldwell-Clements, Inc., New York, 1946, pages 298 to 300, for example.

rThe drive shaft of motor 90` is connected through gears 95 and 96 to a drum 97. A wire 98 is attached to a rocker arm 99 which is connected to the base 100 upon which block 76 rotates. Wire 98 extends from nected by a conduit 112 to the inlet of a valve 113. The drum 97. Rotation of drum 97 thus results in block 76 being rotated about its pivot point. The drive shaft of motor 90 is also connected to the contactor of a telemetering potentiometer 105. A voltage source 106 iS connected across the end terminals of potentiometer 105. The contactor and one end terminal of potentiometer 185 are connected to the input terminals of a controller 137. Controller 107 can be a conventional instrument which provides a regulated output air pressure which is a function of an input electrical signal. This output air pressure can be employed to actuate valve 51 of Figure 1.

The sample stream removed from column 35 of Figure l is directed through conduit 53 which communicates with the inlet of a pressure regulator 110. The outlet of pressure regulator 110 is connected by a conduit 111 to thc inlet of chamber 67. The outlet of chamber 67 is connected by a conduit 112 to the inlet of a valve 113. The outlet of valve 113 is connected to vent conduit 55. A reference fluid -is supplied by a conduit 115 which communicates with the inlet of a pressure regulator 116. The outlet of pressure regulator 116 is connected by a conduit 117, which has a valve 118 therein, to the inlet of chamber 68. The outlet of chamber 68 is connected by a conduit 120 to the inlet of valve 113.

The refractive index measurement is made by comparing the refractive index of the sample stream with the refractive index of a reference fluid. Both of these fluids are maintained in the gaseous state. It is desirable that the sample gas be maintained at a relatively high pressure to provide greater sensitivity. A pressure of approximately 300 pounds per square inch can be employed to advantage, for example. Pressure regulator 110 thus maintains the sample stream circulated through chamber 67 at this pressure. The reference fluid in chamber 68 can be a portion of the final ethylene product from the separation system. This material is applied to the inlet of pressure regulator 116 at a pressure approximately 315 pounds per square inch. Pressure regulator 116 and valve 118 thus function as a flow regulator. If the ow through valve 113 is greater than the tlow through valve 118 and chamber 68, there is n flow through chamber 67. Flow control system 110 and 113 must be set to flow a sample rate larger than through chamber 68. The material in chamber 68 can remain stationary, however.

If the refractive index of the uid in chamber 67 is the same as the refractive index of the fluid in chamber 68, the light beam emerging from cell assembly 66 is parallel to the light beam which enters the cell assembly. Any change in refractive index of the sample fluid results in a deviation of the direction of the emerging light beam. The servo system operates so that the light beam impinges upon the apex of prism 77. This results in equal output voltages being provided by cells 78 and 79 so that the differential output voltage is zero. Motor 90 thus remains stationary. If the light beam should deviate in either direction, one of the photovoltaic cells receives a greater amount of radiation than the other. This results in an output signal which drives, motor 90 to rotate drum 97. The direction of rotation is such as to rotate block 76 in a direction to move the light beam back to the apex of prism 77. The amount of motor rotation is thus representative of changes in the refractive index of the sample iluid. This rotation is applied as a corresponding electrical signal to the input of controller 107.

As a specific example of the operation of the thermal cracking process of this invention, a feed stream of normal butane is introduced into furnace 12 through conduit 10. For each one thousand mols of feed gas, 249 mols of water in the form of steam are added through conduit 13. The resulting mixture is introduced into furnace 12 at a temperature of approximately 150 F. and at a pressure of approximately 85 pounds per square inch absolute (p.s.i.a.). The residence time of the mixture in pipe 14 is approximately 7 seconds and the residence time in pipe 15 is approximately 4 seconds. The gases are heated in pipe 14 to a temperature of approximately l000 F. and are further heated in pipe 15 to a temperature of approximately 1500 F. The ellluent gases leave furnace 12 at a temperature of approximately l500 F. and at a pressure of approximately 20 p.s.i.a. The effluent from furnace 12 has a composition approximately as follows:

Mols per 1000 Material: mols feed gas Hydrogen 200 Methane 830 Acetylene 10 Ethylene 640 Ethane 130 Propylene 250 Propane 12 Butadiene 20 Butylene 25 Normal butane 42 Benzene 48 Water 249 Other compounds 43 Absorber 29 is operated so that nearly all of the C3 and lighter constituents are removed overhead and nearly all of the C4 and heavier constituents are absorbed by the oil. The composition of the fluid mixture in the lower region of column 35 is approximately as follows:

methane and other components of higher boiling points into a first stream substantially free of methane and a second stream containing methane and any components present in the fluid mixture which have boiling points lower than the boiling point of methane which comprises a fractionation column, means to introduce the fluid mixture to be separated into said column, means to withdraw a first stream from the lower region of said column, an accumulator, a condenser, means to pass vapors from the upper region of said column through said condenser to said accumulator, means to return liquid from said accumulator to said column as reflux, means to Withdraw a sample stream from the lower region of said column, means to measure the refractive index of said sample stream, means to withdraw vapor from said accumulator as a second stream, and means responsive to said means to measure to regulate the rate of withdrawal of 'said second stream so that the rate of withdrawal is increased of the measured refractive index decreases `and is decreased if the measured refractive index increases.

2. Apparatus for separating a fluid mixture containing methane and other components of higher boiling points into a first stream substantially free of methane and a second stream containing methane and any components present in the fluid mixture which have boiling points lower than the boiling point of methane which comprises a fractionation column, means .to introduce the fluid mixture to be separated into said column, means to Withdraw a first stream froml the lower region of said column, an accumulator, a condenser, means to pass vapors from the upper region of isaid column through said condenser to said accumulator, means to return liquid from said accumulator to said column as reflux, a liquid-vapor sepa- Theoretical Trays (22 Total) In Figure 3 the index of refraction of the fluid mixture at these several trays is plotted against tray number. The methane concentration at the same trays is also plotted.

It can be seen that the two curves have substantially the same shape. Thus, the refractive index of the mixture is representative of the methane content in the lower region of the column. A measurement of refractive index of a sample withdrawn from a lower tray, actual tray two to six, for example, is thus indicative of the methane concentration. Figure 4 shows the ethane concentration varies almost linearly with the refractive index of the mixture. If the measured refractive index decreases, for example, the methane concentration is increased. Valve 51 is then opened further to permit a greater withdrawal of overhead gas. Conversely, valve 51 is closed further if the measured refractive index increases.

interferences which might be expected are not objectionable because of the relatively large change in methane concentration per tray. For example, at 10% methane, a variation as much as 80% in the ethylene-ethane ratio is indicated as only a 1% change inmethane concentration. The heavier components are present in very small quantities so that changes in concentration thereof are relatively unimportant.

While the invention has been described in conjunction m'th present preferred embodiments, it obviously is not limited thereto.

What is claimed is:

l. Apparatus for separating a fluid mixture containing rator, valved conduit'means communicating between the upper region of said accumulator and said separator, the valve in vsaid conduit means resulting in a substantial pressure drop of the vapor delivered to said separator to condense a portion thereof, means to Withdraw vapor Vfrom said separator as a second stream, means to withdraw a sample stream from the lower region of said column, means to measure the refractive index of said ysample stream, and means responsive to said means to measure to regulate the rate of withdrawal of said second stream so that the rate of withdrawal is increased if the measured refractive index decreases and is `decreased if the measured refractive index increases.

3. Apparatus for :separating a fluid mixture containing methane and other components of Ihigher boiling points into a first stream substantially free of methane and a second stream containing methane and any components present in the fluid mixture which have boiling points lower lthan the boiling boint of methane which comprises a fractionation column, means to introduce the fluid mixture to be separated into said column, means to withdraw a rst stream from the lower region of said column, an accumulator, a condenser, means to pass vapors from the upper region of said column through said condenser to said accumulator, means to return liquid from said accumulator to said column as reflux, a liquid-vapor separator, first and second heat exchange means, a valve, first conduit means communicating between the upper region of said accumulator and said separator through said first and second heat exchange means and said valve, said valve resulting in a substantial pressure drop of the vapor delivered to said separator to condense a portion thereof, second conduit means' to pass liquid from said separator through said first heat exchange means to said accumulator, third' conduit means to withdraw vapor from said separator as a second stream, said third conduit means passing through said second heat exchange means, means to withdraw a sampley stream from the lower region of said column, means to measure the refractive index of said sample stream, and means responsive to said means to measure to regulate the rate of withdrawal of said second stream so that the rate of withdrawal is increased if the measured refractive index decreases and is decreased if the measured refractive index increases.

4. The combination in accordance with claim l wherein said means to measure refractive index cornpriscs a first sample cell having transparent windows, a second sample cell having transparent windows, means for directing avbe'am of radiation successively through said first and second cells, a radiation transparent plate dividing s aidV cells7 the plane of said plate making an angle other than 90 with the direction of said beam of radiation, means to circulate said sample stream through one of said cells, means to position a reference uid in the other of said cells, and means to measure the deviation of saidradiation beam passed through said first and second cells, said deviation being representative of the difference in refractive indices of fiuidsA in said two cells.

5. Apparatus for separating a fluid mixture containing methane and other components of high boiling points into a first stream substantially free of methane and a second stream containing methane and any components present in the fluid mixture which have boiling points lower than the boiling point of methane whichV comprises a fractionation column, means to introduce the uid mixture to be separated into said column, means to withdraw a first stream from the lower region of said column, an accumulator, a condenser, meansto pass vapors from the upper region of said column through said condenser to said accumulator, means to return liquid from said accumulator to said column as reux, a rst cell having transparent windows, a second cell having transparent windows, means for directing beam.

of radiation successively through said first and second cells, a radiation transparent plate dividing said cells, the plane of said plate making an angle other than 90 with the direction of said beam of radiation, a first pressure regulator, means to withdraw a sample stream from the lower region of said column and to pass same to the inlet of said first pressure regulator, a first conduit communicating between the outlet of said first pressure regulator and the inlet of one of said cells, a second conduit communicating with the outlet of said one cell, a first valve in said second conduit, a second pressure regulator, the inlet of said second pressure regulator being adapted to be' connected to a source of reference uid, a third conduit communicating between the outlet of said second' pressure regulator and the inlet of the other of said cells, a second valve in said third conduit, a fourth conduit communicating between the outlet of said other cell and said second conduit between said first valve and said one cell, and means to measure the deviation of the radiation beam passed through said first and second cells, said deviation being representative of the difference in refractive indices of fluids in said two cells, and means responsive to said means to measure to regulate the rate of withdrawal of said second stream so that the rate of withdrawal is increased as the measured refractive index decreases andv is decreased as the measured refractive indexrv increases.

6. The combination in accordance with claim 5 further comprising a source' of ethane under pressre greater than atmospheric communicating with the inlet of said second pressure regulator.

7. Apparatus for separating a fluid mixture containing methane and other components of higher boiling points into a first stream substantially free of methane and a second stream containing methane and any components present in th'e uid mixture which have boiling points lower than the' boiling point of methane which comprises a fractionation column, means to introduce the fluid mixture to be separated into said column, means to withdraw a first stream from the lower region of said column, means to withdraw a second stream from the upper region` of said column, means to withdraw a sample stream from the lower region of said column, means to measure the refractive index of said sample stream, and means responsiveto said means to measure to regulate the rate of withdrawal of said second stream so that the rate of withdrawal is increased if the measured refractive index decreases and is decreased if the measured refractive index increases.

References Cited in the file of this patent UNITED STATES PATENTS 1,961,201 De Baufre June 5, 1934 2,501,999 Fausek Mar. 28, 1950 2,612,814 Glasser Oct. 7, 1952 2,624,014 Barstow Dec. 30, 1952 2,627,318 Swerdlot Feb. 3, 1953 2,649,013 Schnelle Aug. 18, 1953 2,471,941 Madsen Apr. 17, 1956 2,750,511 Miller June 12, 1956 UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No.. 2,890,571 June 1.6, 1959 Elmer C., Miller It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column l, line 33, for fluix read fluid ne; column A, line 3,

after "from" insert =f rocker arm 99 about guide wheels lOl, 102, and 103 and drum 97., lines 4. and 5, strike out nested by Conduit 112 to the inlet of a valve 113, The drum 97.,"3 Column line 1F51, for "of Signed and sealed this 19th day of January 19600 Attest: l r EARL E. AXLTNE ROBERT C. WATSON f Commissioner Of Patents Attesting Officer 

1. APPARATUS FOR SEPARATING A FLUID MIXTURE CONTAINING METHANE AND OTHER COMPONENTS OF HIGHER BOILING POINTS INTO A FIRST STREAM SUBSTANTIALLY FREE OF METHANE AND A SECOND STEAM CONTAINING METHANE AND ANY COMPONENTS PRESENT IN THE FLUID MIXTURE WHICH HAVE BOILING POINTS LOWER THAN THE BOILING POINT OF METHANE WHICH COMPRISES A FRACTIONATION COLUMN, MEANS TO INTRODUCE THE FLUID MIXTURE TO BE SEPARATED INTO SAID COLUMN, MEAND TO WITHDRAW A FIRST STREAM FROM THE LOER REGION OF SAID COLUMN, AN ACCUMULATOR, A CONDENSER, MEANS TO PASS VAPORS FROM THE UPPER REGION OF SAID COLUMN THROUGH SAID CONDENSER TO SAID ACCUMULATOR, MEANS TO RETURN LIQUID FROM SAID ACCUMULATOR TO SAID COUMN AS REFLUX, MEANS TO WITHDRAW A SAMPLE STREAM FROM THE LOWER REGION OF SAID COLUMN, MEANS TO MEASZURE TH EREFRACTIVE INDEX OF SAID SAMPLE STREAM, MEANS TO WITHDRAW VAPOR FRM SAID ACCUMULATOR AS A SECOND STREAM, AND MEANS RESPONSIVE TO SAID MEANS TO MEASURE TO REGULATE THE REAT OF WITHDRAWAL OF SAID SECOND STREAM SO THAT THE RATE OFG WITHDRAWAL IS INCREASED AS THE MEASURED REFRACTIVE INDEX DECREASES AND IS DECREASED IF THE MEASURED REFRACTIVE INDEX INCREASES. 